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US4560444A Expired / Lapsed US ⏱️ 0.0 years remaining

Gas detection with novel electrolyte membrane and solid internal reference

Assignee: Honeywell UOP LLC
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Filing: 1983-12-29
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Granted: 1985-12-24
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Expires: 2003-12-29
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Abstract

Abstract Apparatus and method for detecting and measuring hydrogen and compounds capable of dissociating into or combining with hydrogen ions using a solid electrolyte concentration cell. A solid reference substance is used in place of a reference gas. A novel solid electrolyte membrane is used which comprises an organic polymer-inorganic compound blend prepared by admixing an organic polymer such as poly(vinyl alcohol) with a heteropoly acid or salt thereof such as dodecamolybdophosphoric acid or uranyl orthophosphate in a mutually miscible solvent.

Inventors

  • 👤 Anthony J. Polak
  • 👤 Allyson J. Beuhler

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-05 10:34
CPC Classifications
G; G01; G01N; G01N27/00; G01N27/26; G01N27/403; G01N27/406; G01N27/407; G01N27/4073; G01N27/4074; G01N27/4075; G01N27/4076

Claims Analysis

Total Claims: 21
Claim 1
Independent Claim 401 words
An apparatus for detection, in a gas sample, of a gaseous component, which is capable, in the presence of a catalytic agent, of dissociating to yield hydrogen ions or of combining with hydrogen ions, which apparatus comprises: (a) a thin film organic-inorganic membrane which comprises a blend of: (1) from about 10% to about 70% by weight of a heteropoly acid and salts thereof having the generic formula: A.sub.m [X.sub.x Y.sub.y O.sub.z ]. nH.sub.2 O in which X is selected from the group consisting of boron, aluminum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, iodine, and metals of the first, second, third and fourth transitional metal series of the Periodic Table and where Y is dissimilar from X and is selected from at least one metal of the first, second, third and fourth transitional metal series of the Periodic Table, A is selected from the group consisting of hydrogen, ammonium, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, m is an integer of from about 1 to 10, y is a integer of from 6 to 12 based on x being equal to 1, z is an integer of from 30 to 80 and n is an integer of from 3 to 100 and, (2) from about 90% to about 30% by weight of a polymer compatible with said compound selected from the group consisting of poly (vinyl alcohol), poly (vinyl fluoride), polyethylene oxide, polyethyleneimine, polyacrylic acid, polyethylene glycol, cellulose acetate, polyvinylmethylethyl ether and phenol formaldehyde resins; (b) an organic-inorganic membrane housing comprising a sample gas chamber and a reference chamber separated by a substantially imporous partition comprising said organic-inorganic membrane, said membrane having a first surface in common with the sample gas chamber and a second surface in common with the reference chamber; (c) two separate portions of catalytic agent effective to promote dissociation and combination, a first portion in contact with said first surface and a second portion in contact with said second surface of said membrane; (d) a reference substance in said reference chamber and in contact with said second catalytic agent portion, which substance exhibits a substantially constant known hydrogen partial pressure during use of said detection apparatus; and, (e) means for forming electrical connection in operative contact with said first portion of catalytic agent at said first surface and with said second portion of catalytic agent at said second surface.
Claim 2
Independent Claim 401 words
An apparatus for detection, in a gas sample, of a gaseous component, which is capable, in the presence of a catalytic agent, of dissociating to yield hydrogen ions or of combining with hydrogen ions, which apparatus comprises: (a) a thin film organic-inorganic membrane which comprises a blend of: (1) from about 10% to about 70% by weight of a heteropoly acid and salts thereof having the generic formula: A.sub.m [X.sub.x Y.sub.y O.sub.z ]. nH.sub.2 O in which X is selected from the group consisting of boron, aluminum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, iodine, and metals of the first, second, third and fourth transitional metal series of the Periodic Table and where Y is dissimilar from X and is selected from at least one metal of the first, second, third and fourth transitional metal series of the Periodic Table, A is selected from the group consisting of hydrogen, ammonium, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, m is an integer of from about 1 to 10, y is a integer of from 6 to 12 based on x being equal to 1, z is an integer of from 30 to 80 and n is an integer of from 3 to 100 and, (2) from about 90% to about 30% by weight of a polymer compatible with said compound selected from the group consisting of poly (vinyl alcohol), poly (vinyl fluoride), polyethylene oxide, polyethyleneimine, polyacrylic acid, polyethylene glycol, cellulose acetate, polyvinylmethylethyl ether and phenol formaldehyde resins; (b) an organic-inorganic membrane housing comprising a sample gas chamber and a reference chamber separated by a substantially imporous partition comprising said organic-inorganic membrane, said membrane having a first surface in common with the sample gas chamber and a second surface in common with the reference chamber; (c) two separate portions of catalytic agent effective to promote dissociation and combination, a first portion in contact with said first surface and a second portion in contact with said second surface of said membrane; (d) a reference substance in said reference chamber and in contact with said second catalytic agent portion, which substance exhibits a substantially constant known hydrogen partial pressure during use of said detection apparatus; and, (e) means for forming electrical connection in operative contact with said first portion of catalytic agent at said first surface and with said second portion of catalytic agent at said second surface.
Claim 3
Dependent Claim 25 words
The apparatus of claim 1 further characterized in that said catalytic agent is selected from a group consisting of platinum, nickel, palladium, and alloys thereof.
Claim 4
Dependent Claim 15 words
The apparatus of claim 1 further characterized in that said catalytic agent is electrically conductive.
Claim 5
Dependent Claim 18 words
The apparatus of claim 1 further characterized in that said catalytic agent is porous to said gaseous component.
Claim 6
Dependent Claim 17 words
The apparatus of claim 1 further including means to adjust the operating temperature of said membrane housing.
Claim 7
Dependent Claim 17 words
The apparatus of claim 1 further including means to supply sample gas to the sample gas chamber.
Claim 8
Dependent Claim 19 words
The apparatus of claim 1 further including means to measure EMF connected between said means for forming electrical connection.
Claim 9
Dependent Claim 15 words
The apparatus of claim 7 further including means to convert said EMF measurement to concentration.
Claim 10
Dependent Claim 20 words
The apparatus of claim 1 in which said membrane possesses a thickness of from about 0.1 to about 50 microns.
Claim 11
Dependent Claim 19 words
The apparatus of claim 1 in which said polymer comprises poly(vinyl alcohol) and said heteropoly acid comprises dodecamolybdophosphoric acid.
Claim 12
Dependent Claim 16 words
The apparatus of claim 1 further characterized in that said reference substance is a metal hydride.
Claim 13
Dependent Claim 20 words
The apparatus of claim 1 further characterized in that a single substance serves as both reference substance and catalytic agent.
Claim 14
Dependent Claim 18 words
The apparatus of claim 1 further characterized in that said reference substance and catalytic agent is palladium hydride.
Claim 15
Independent Claim 348 words
A method of detecting, in a gas sample, a gaseous component capable, in the presence of a catalytic agent, of dissociating to yield hydrogen ions or of combining with hydrogen ions, said method comprises: (a) contacting said gas sample with a first surface of an imporous thin film organic-inorganic membrane comprising a blend of: (1) from about 10% to about 70% by weight of a heteropoly acid and salts thereof having the generic formula: A.sub.m [X.sub.x Y.sub.y O.sub.z ] .nH.sub.2 O in which X is selected from the group consisting of boron, aluminum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, iodine, and metals of the first, second, third and fourth transitional metal series of the Periodic Table and where Y is dissimilar from X and is selected from at least one metal of the first, second, third and fourth transitional metal series of the Periodic Table, A is selected from the group consisting of hydrogen, ammonium, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, m is an integer of from about 1 to 10, y is an integer of from 6 to 12 based on x being equal to 1, z is an integer of from 30 to 80 and n is an integer of from 3 to 100 and, (2) from about 90% to about 30% by weight of a polymer compatible with said compound selected from the group consisting of poly (vinyl alcohol), poly (vinyl fluoride), polyethylene oxide, polyethyleneimine, polyacrylic acid, polyethylene glycol, cellulose acetate, polyvinylmethyethyl ether and phenol formaldehyde resins having a first portion of catalytic agent in contact therewith effective to promote dissociation and combination; (b) contacting a reference substance which exhibits a substantially constant known hydrogen partial pressure, with a second surface of said organic-inorganic membrane of step (a) having a second portion of catalyst in contact therewith; and, (c) detecting EMF between means for forming electrical connection in operative contact with said first portion of catalytic agent at said first surface and with said second portion of catalytic agent at said second surface of said membrane.
Claim 16
Independent Claim 348 words
A method of detecting, in a gas sample, a gaseous component capable, in the presence of a catalytic agent, of dissociating to yield hydrogen ions or of combining with hydrogen ions, said method comprises: (a) contacting said gas sample with a first surface of an imporous thin film organic-inorganic membrane comprising a blend of: (1) from about 10% to about 70% by weight of a heteropoly acid and salts thereof having the generic formula: A.sub.m [X.sub.x Y.sub.y O.sub.z ] .nH.sub.2 O in which X is selected from the group consisting of boron, aluminum, gallium, silicon, germanium, tin, phosphorus, arsenic, antimony, bismuth, selenium, tellurium, iodine, and metals of the first, second, third and fourth transitional metal series of the Periodic Table and where Y is dissimilar from X and is selected from at least one metal of the first, second, third and fourth transitional metal series of the Periodic Table, A is selected from the group consisting of hydrogen, ammonium, sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, m is an integer of from about 1 to 10, y is an integer of from 6 to 12 based on x being equal to 1, z is an integer of from 30 to 80 and n is an integer of from 3 to 100 and, (2) from about 90% to about 30% by weight of a polymer compatible with said compound selected from the group consisting of poly (vinyl alcohol), poly (vinyl fluoride), polyethylene oxide, polyethyleneimine, polyacrylic acid, polyethylene glycol, cellulose acetate, polyvinylmethyethyl ether and phenol formaldehyde resins having a first portion of catalytic agent in contact therewith effective to promote dissociation and combination; (b) contacting a reference substance which exhibits a substantially constant known hydrogen partial pressure, with a second surface of said organic-inorganic membrane of step (a) having a second portion of catalyst in contact therewith; and, (c) detecting EMF between means for forming electrical connection in operative contact with said first portion of catalytic agent at said first surface and with said second portion of catalytic agent at said second surface of said membrane.
Claim 17
Dependent Claim 15 words
The method of claim 14 further characterized in that said gaseous component is elemental hydrogen.
Claim 18
Dependent Claim 15 words
The method of claim 14 further characterized in that said gaseous component is elemental oxygen.
Claim 19
Dependent Claim 22 words
The method of claim 14 further characterized in that water is added to said gas sample before the gas contacts said membrane.
Claim 20
Dependent Claim 26 words
The method of claim 14 further characterized in that the concentration of said gaseous component in the sample is adjusted before the sample contacts said membrane.
Claim 21
Dependent Claim 23 words
The method of claim 14 further characterized in that the temperature of said gas sample is adjusted before said gas contacts said membrane.

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USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1988-12-23 1989-06-24 1989-12-24 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1992-12-23 1993-06-24 1993-12-24 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1996-12-23 1997-06-24 1997-12-24 $7700.00 Window Closed / Lapsed

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